EP2215142B1 - Solventless processes for the polymerization of a trimethylene carbonate to a poly(trimethylene glycol carbonate trimethylene glycol ether) diol - Google Patents
Solventless processes for the polymerization of a trimethylene carbonate to a poly(trimethylene glycol carbonate trimethylene glycol ether) diol Download PDFInfo
- Publication number
- EP2215142B1 EP2215142B1 EP08855247A EP08855247A EP2215142B1 EP 2215142 B1 EP2215142 B1 EP 2215142B1 EP 08855247 A EP08855247 A EP 08855247A EP 08855247 A EP08855247 A EP 08855247A EP 2215142 B1 EP2215142 B1 EP 2215142B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- carbonate
- trimethylene
- trimethylene glycol
- poly
- diol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Not-in-force
Links
- YFHICDDUDORKJB-UHFFFAOYSA-N trimethylene carbonate Chemical compound O=C1OCCCO1 YFHICDDUDORKJB-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 22
- -1 poly(trimethylene glycol carbonate trimethylene glycol Chemical compound 0.000 title claims abstract description 21
- 150000002009 diols Chemical class 0.000 title claims abstract description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000006116 polymerization reaction Methods 0.000 title abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 125000001424 substituent group Chemical group 0.000 claims description 10
- 125000004122 cyclic group Chemical group 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 4
- 125000006737 (C6-C20) arylalkyl group Chemical group 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 2
- SELFXCFVPOJKBE-UHFFFAOYSA-N 2-(1-ethenoxypropan-2-yloxy)ethanesulfonic acid Chemical compound C=COCC(C)OCCS(O)(=O)=O SELFXCFVPOJKBE-UHFFFAOYSA-N 0.000 claims description 2
- 239000003456 ion exchange resin Substances 0.000 claims description 2
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 2
- 239000011973 solid acid Substances 0.000 abstract description 5
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 13
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 11
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 11
- 239000000463 material Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 6
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- 229920000557 Nafion® Polymers 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 3
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 2
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- LVZWSLJZHVFIQJ-UHFFFAOYSA-N Cyclopropane Chemical compound C1CC1 LVZWSLJZHVFIQJ-UHFFFAOYSA-N 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000002877 alkyl aryl group Chemical group 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000002306 biochemical method Methods 0.000 description 2
- 239000012620 biological material Substances 0.000 description 2
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 2
- 239000004914 cyclooctane Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229920001692 polycarbonate urethane Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 102000004882 Lipase Human genes 0.000 description 1
- 108090001060 Lipase Proteins 0.000 description 1
- 239000004367 Lipase Substances 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- RIFGWPKJUGCATF-UHFFFAOYSA-N ethyl chloroformate Chemical compound CCOC(Cl)=O RIFGWPKJUGCATF-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/30—General preparatory processes using carbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/02—Aliphatic polycarbonates
- C08G64/0208—Aliphatic polycarbonates saturated
Definitions
- This invention relates to solventless processes for the polymerization of trimethylene carbonates to a poly(trimethylene glycol carbonate trimethylene glycol ether) diols, the process using one or more solid acid catalysts.
- poly(trimethylene glycol carbonate trimethylene glycol ether) diol can be used in a number of applications, including but not limited to biomaterials, engineered polymers, personal care materials, coatings, lubricants and polycarbonate/polyurethanes (TPUs).
- the initiating agent becomes incorporated into the polymer ends.
- One aspect of the present invention is a process for making a poly(trimethylene glycol carbonate trimethylene glycol ether) diol of structure wherein z is an integer of 1 to 10; n is an integer of 2 to 100; and each R substituent is independently selected from the group consisting of H, C 1 -C 20 alkyl, C 3 -C 20 cyclic alkyl, C 5 -C 25 aryl, C 6 -C 20 alkaryl, and C 6 -C 20 arylalkyl, and wherein each R substituent can optionally form a C 3 -C 8 cyclic structural group (for example, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane and cyclooctane) with adjacent R substituents; the process comprising: contacting trimethylene carbonate or an R-substituted trimethylene carbonate with a solid acid catalyst at a temperature greater than the melting point of the trimethylene
- the temperature is about 30 degrees Celsius or greater.
- the present invention relates to a process to make a poly(trimethylene glycol carbonate trimethylene glycol ether) diol from a trimethylene carbonate (TMC, 1,3-dioxan-2-one) at elevated temperature (generally 30 to 250 degrees Celsius) polymerization, in the absence of solvent, utilizing a solid acid catalyst.
- TMC trimethylene carbonate
- TMC trimethylene carbonate
- the reaction can be represented by the equation below:
- each R substituent is independently selected from the group consisting of H, C 1 -C 20 alkyl, particularly C 1 -C 6 alkyl, C 3 -C 20 cyclic alkyl, C 3 -C 6 cyclic alkyl, C 5 -C 25 aryl, particularly C 5 -C 11 aryl, C 6 -C 20 alkaryl, particularly C 6 -C 11 alkaryl, and C 6 -C 20 arylalkyl, particularly C 6 -C 11 arylalkyl, and each R substituent can optionally form a cyclic structural group with adjacent R substituents.
- cyclic structural groups are C 3 -C 8 cyclic groups, e.g., cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, and cyclooctane.
- n is an integer of 2 to 100, and particularly 2 to 50; and z is an integer of 1 to 20, particularly 1 to 7, more particularly 1 to 5.
- the poly(trimethylene glycol carbonate trimethylene glycol ether) diol can be isolated using known methods.
- TMC is prepared by any of the various chemical or biochemical methods known to those skilled in the art.
- Chemical methods for the preparation of TMC include, but are not limited to, a) reacting 1,3-propanediol with diethylcarbonate in the presence of zinc powder, zinc oxide, tin powder, tin halide or an organotin compound at elevated temperature , b) reacting 1,3-propanediol and phosgene or bis-chloroformates to produce a polycarbonate intermediate that is subsequently depolymerized using heat and, optionally, a catalyst, c) depolymerizing poly(trimethylene carbonate) in a wiped film evaporator under vacuum, d) reacting 1,3-propanediol and urea in the presence of metal oxides, e) dropwise addition of triethylamine to a solution of 1,3-propanediol and ethylchloroformate in THF, and
- Biochemical methods for the preparation of TMC include, but are not limited to, a) lipase catalyzed condensation of diethylcarbonate or dimethylcarbonate with 1,3-propanediol in an organic solvent, and b) lipase-catalyzed depolymerization of poly(trimethylene carbonate) to produce TMC.
- the 1,3-propanediol and/or trimethylene carbonate (TMC) can be obtained biochemically from a renewable source ("biologically-derived" 1,3-propanediol).
- the 1,3-propanediol used as the reactant or as a component of the reactant will have a purity of greater than about 99%, and more preferably greater than about 99.9%, by weight as determined by gas chromatographic analysis.
- the 1,3-propanediol preferably has the following characteristics:
- the solid acid resins useful as catalysts in the processes disclosed herein include the sulfonated tetrafluoroethylene copolymers NAFION® NR50 (tetrafluoroethylene/perfluoro(4-methyl-3,6-dioxa-7-octene-1-sulfonic acid) copolymer, an ionomer available from E.I. DuPont de Nemours Company, Wilmington, DE. .
- the processes disclosed herein are desirably carried out substantially or totally in the absence of a solvent ("solventless").
- the process described herein occurs at elevated temperature, generally above the melting point of the monomers used, typically from about 30 to 250 degrees Celsius, and frequently about 50 to 150 degrees Celsius, preferably about 100 to 150 degrees Celsius.
- the reactants may be mixed by any convenient method.
- the process can be done in batch, semi-batch or continuous mode, and generally take place in an inert atmosphere (i.e., under nitrogen).Once the reactants have been contacted with the catalyst, the reaction is allowed to continue for the desired time.
- at least 6 percent of the TMC polymerizes to give the desired poly(trimethylene glycol carbonate trimethylene glycol ether) diol after about 3 to 6 hours, with greater than about 75 percent conversion achieved within about 25 hours.
- 100 percent conversion is easily achieved by the proper selection of catalyst, the amount of catalyst, and the reaction temperature and time.
- n is an integer generally between 2 and 100, and more specifically between 2 and 50; and z is 1 to 20, more specifically between 1 and 10.
- the resulting poly(trimethylene glycol carbonate trimethylene glycol ether) diols are easily separated from the unreacted starting materials and catalyst by any convenient means, such as filtration, including filtration after concentration.
- the processes disclosed herein allow for the degree of polymerization to be selected based on the solvent and/or catalyst chosen, and the amount of those materials used. This is advantageous as the materials resulting from the process can vary in properties including viscosity, and can find wide uses in products such as personal care, coatings (including thermoplastic polyurethanes), elastomers and lubricants.
- the diol produced can find wide uses in products such as biomaterials, engineered polymers, personal care materials, coatings, lubricants and polycarbonate/polyurethanes (TPUs).
- each R is independently selected from the group consisting of H, C 1 -C 20 alkyl, particularly C 1 -C 6 alkyl, C 3 -C 20 cyclic alkyl, C 3 -C 6 cyclic alkyl, C 5 -C 25 aryl, particularly C 5 -C 11 aryl, C 6 -C 20 alkaryl, particularly C 6 -C 11 alkaryl, and C 6 -C 20 arylalkyl, particularly C 6 -C 11 arylalkyl, and each R substituent can optionally form a cyclic structure with adjacent R substituents.
- n is an integer of 2 to 100, and more particularly 2 to 50; and z is an integer of 1 to 10, particularly 1 to 7, more particularly 1 to 5.
- the DSC runs were made on a TA Instruments Q2000 DSC, using a 10°C/min heating rate and an N 2 purge. The profile used was heat, cool and reheat from -90 to 100°C.
- the TGA runs were made on a TA Instruments Q5000 TGA, again using a 10°C/min heating rate and an N 2 purge.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US99168707P | 2007-11-30 | 2007-11-30 | |
| PCT/US2008/084693 WO2009070587A1 (en) | 2007-11-30 | 2008-11-25 | Solventless processes for the polymerization of a trimethylene carbonate to a poly(trimethylene glycol carbonate trimethylene glycol ether) diol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP2215142A1 EP2215142A1 (en) | 2010-08-11 |
| EP2215142B1 true EP2215142B1 (en) | 2011-12-21 |
Family
ID=40350063
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP08855247A Not-in-force EP2215142B1 (en) | 2007-11-30 | 2008-11-25 | Solventless processes for the polymerization of a trimethylene carbonate to a poly(trimethylene glycol carbonate trimethylene glycol ether) diol |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US7790833B2 (enExample) |
| EP (1) | EP2215142B1 (enExample) |
| JP (1) | JP2011505468A (enExample) |
| KR (1) | KR20100102629A (enExample) |
| CN (1) | CN101878244A (enExample) |
| AT (1) | ATE538159T1 (enExample) |
| AU (1) | AU2008329778A1 (enExample) |
| BR (1) | BRPI0818996A2 (enExample) |
| CA (1) | CA2704022A1 (enExample) |
| ES (1) | ES2378359T3 (enExample) |
| MX (1) | MX2010005754A (enExample) |
| TW (1) | TW200934807A (enExample) |
| WO (1) | WO2009070587A1 (enExample) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2703786A1 (en) * | 2007-11-30 | 2009-06-04 | E.I. Du Pont De Nemours And Company | Process to make a poly(trimethylene carbonate) glycol |
| KR20100099713A (ko) * | 2007-11-30 | 2010-09-13 | 이 아이 듀폰 디 네모아 앤드 캄파니 | 폴리(트라이메틸렌 글리콜 카보네이트 트라이메틸렌 글리콜 에테르) 다이올 조성물 및 이의 제조 방법 |
| KR101202510B1 (ko) | 2010-10-20 | 2012-11-20 | 삼성메디슨 주식회사 | 위상 배열 프로브에 기초하여 초음파 공간 합성 영상을 제공하는 초음파 시스템 및 방법 |
| WO2025197815A1 (ja) * | 2024-03-19 | 2025-09-25 | 富士フイルム株式会社 | ポリカーボネート化合物の製造方法 |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05339360A (ja) * | 1992-06-12 | 1993-12-21 | Idemitsu Petrochem Co Ltd | ポリカーボネートの製造方法 |
| DE69317818T2 (de) * | 1992-07-13 | 1998-08-06 | Tosoh Corp | Verfahren zur Herstellung von tertiären Alkoholen |
| JPH0710920A (ja) * | 1992-12-01 | 1995-01-13 | Nippon Paint Co Ltd | 環状カーボネート化合物のアルコール性水酸基への開環付加方法 |
| JPH09176152A (ja) * | 1995-12-28 | 1997-07-08 | Sumitomo Bakelite Co Ltd | 環状カーボナート化合物の重合方法 |
| US6451949B2 (en) * | 2000-02-29 | 2002-09-17 | Shell Oil Company | Method for production of poly (trimethylene carbonate) |
| KR20100099713A (ko) * | 2007-11-30 | 2010-09-13 | 이 아이 듀폰 디 네모아 앤드 캄파니 | 폴리(트라이메틸렌 글리콜 카보네이트 트라이메틸렌 글리콜 에테르) 다이올 조성물 및 이의 제조 방법 |
| WO2009070578A1 (en) * | 2007-11-30 | 2009-06-04 | E. I. Du Pont De Nemours And Company | Copolymers comprising a trimethylene carbonate and poly(trimethylene ether) glycols |
-
2008
- 2008-11-25 AU AU2008329778A patent/AU2008329778A1/en not_active Abandoned
- 2008-11-25 EP EP08855247A patent/EP2215142B1/en not_active Not-in-force
- 2008-11-25 CN CN2008801183093A patent/CN101878244A/zh active Pending
- 2008-11-25 JP JP2010536129A patent/JP2011505468A/ja active Pending
- 2008-11-25 KR KR1020107014392A patent/KR20100102629A/ko not_active Withdrawn
- 2008-11-25 AT AT08855247T patent/ATE538159T1/de active
- 2008-11-25 CA CA2704022A patent/CA2704022A1/en not_active Abandoned
- 2008-11-25 US US12/277,644 patent/US7790833B2/en not_active Expired - Fee Related
- 2008-11-25 ES ES08855247T patent/ES2378359T3/es active Active
- 2008-11-25 BR BRPI0818996 patent/BRPI0818996A2/pt not_active IP Right Cessation
- 2008-11-25 MX MX2010005754A patent/MX2010005754A/es active IP Right Grant
- 2008-11-25 WO PCT/US2008/084693 patent/WO2009070587A1/en not_active Ceased
- 2008-11-28 TW TW097146471A patent/TW200934807A/zh unknown
Also Published As
| Publication number | Publication date |
|---|---|
| AU2008329778A1 (en) | 2009-06-04 |
| KR20100102629A (ko) | 2010-09-24 |
| TW200934807A (en) | 2009-08-16 |
| CA2704022A1 (en) | 2009-06-04 |
| ES2378359T3 (es) | 2012-04-11 |
| US20090143564A1 (en) | 2009-06-04 |
| WO2009070587A1 (en) | 2009-06-04 |
| ATE538159T1 (de) | 2012-01-15 |
| MX2010005754A (es) | 2010-06-09 |
| BRPI0818996A2 (pt) | 2015-05-05 |
| US7790833B2 (en) | 2010-09-07 |
| CN101878244A (zh) | 2010-11-03 |
| EP2215142A1 (en) | 2010-08-11 |
| JP2011505468A (ja) | 2011-02-24 |
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